Alkylene oxide-methylol phenol reaction products



i atenteci Aug 12 1 952 t V V v UNITED STATES PATENT omen; Q

ALKYLENE oxmli-Ma'rnfijdrfjfiiifinoi" REACTION PRODUCTS Robert W. Martin',-Lei1ox, Mass); assigndntdiGen' -f eral Electric Company, a corporatiomof- New York i c No Drawing. Application j'anfiaiil 4; 1%"513- Serial No. 2043467- irciaimir; (c1. M41135:- J c This application is a continuation-impart; i} amduntra-nging below" 70%", for example, from my earlierfiled application Serial No. 122,128, abo'utl'0 t90%j, and"(3')' an alkylene'oxide-con filed October 18; 1949 now Patent Nnmber respondin'gitothegeneralformnla 2,579,329, and assigned to thesame assigneeas R1463 H thepresent invention. 5 J

This invention is concerned with novel com 7 I 2H0 positions of matter. More particularly, the in-' e i sie ven ab fiq e, vention relates to the reaction product offa mix- Am ng the gr up W ZRr in fl' he'wflbovc ture of ingredients comprising (1) a methylol r la m yz en es ar -n zin t erel ii phenyl ether corresponding to the general 10 p -i hyhi hylg,P 0D QPIQ yl.' al

I 1y1-, metha-llyl cyclopentenyl, cycloheiieny e cy loh xa y cy 10penin h fl w-:21 nM-sllfi r; tuted iphatic. lar k m i t n e: been! etczt-styryl; etc;.-; as 'weillgas halogenated derivatives; of c the l aforementioned aliphatic groups, for example; the aforementioned groups containing; ch1orine,'-- bromine; 1i1-iorine etcz, either;,ion thealiphatic: or -aromatic grouping-and either mono- ('JHQOH where R represents'ainember of the mess ah-= halogenated or po-lyhal-ogenated for- (again-hie; sisting of aliphatic, cycloaliphatic, and aryl-subcontaining?from"-tw o 'or more'halog --for--ex stituted aliphatic groups including their halo ample, =.chl'orines;etc -in:the organicgroljps gen-substituted derivatives, and (2) an alkylen'e Riflf-addjtiorfltg being jhe 11 at oxide corresponding'to the-general formulaaliphatic-andaryl-snbstitnted ahpha H groups H mentioned'a-boveffor':R may"a1so-he;ar1,' e g O I phenyl; etc; alkoxyaliphaticgelge methggyethyl 1 etho'xymethyl, ethoxybl ytyl, etc:; a where R is a member selected from the class tilted a mtqlyl l consisting of I hydrogen, aliphatic; alkoxyal-igm .v mm j f phatic, aryl, aliphatic-substituted aryl, arm-subaryroxysmiphatic e; g}, mghy hbky; stituted aliphatic, and aryloxyaliphatic radicals; ethylytolyloxypropyhetc; h Q: The invention also includes reaction products; of v t i ifi. majli"b jii fif ga a mixture of ingredients comprising e?" are;forinstance;-those-'-corrspondin"to the gen methylol phenyl ether corresponding-to the genefalifdrmulaf eral formula:-

I 0 R R' I n (I H6 errata-" oon; "OHEOQGH-AZZHOHT L H; H v

I 40 v i I v GHzOH' f" (2) al methylollph'enyl ether corresfionding tothe genera1formula I 4 e a e mac I where'R 'aiidRI have; themeanings' givenabove;

Theposition"of' th'R'" will deiaen'cl onthemann'er in which the alkylene oxide ring reacts. The above disclosedreaction product can be made by "efiectin'g-reaction between the alkylene oxide'and the-"preforn1ed nithi lol phe'n yl ether: derivative (Formula-l). Thereactionis believed where R has the meaning given above, and his fls pw s t "I d ifib b' jtwo an integer equal to from 1 to '2,'inclusive;' and orthree' ofthe'methyl'ol*groups with-the alkyl'ene whereco'mpoundfl) is preferablyin' an amount oxide. Q H equal to" at least 50% but may be present inan 53- In the fol1owingexamp1esg mt s';

closed for preparing the sodium and barium salts of trimethylol phenol which can then be reacted with the appropriate ingredient to give the methylol phenyl ether described above in Formula I. The ether thus obtained or mixtures of ethers which correspond to Formulas I and III may then in turn be reacted with the alkylene oxide defined by Formula II.

The sodium and barium salts of trimethylol phenol may be formed very simply and isolated as crystalline compounds. More particularly, the crystalline sodium and barium salts of trimethylol phenol may be prepared by effecting reaction between about three mols of formaldehyde and one mol of phenol in the presence of about one mol of alkali such as the hydroxides of sodium and barium at a temperature such that no resinous material is formed. This temperature has been found to range up to about 65 0., above which temperature undesired side reactions take place. The salt of trimethylol phenol can then be precipitated by diluting or pouring the reaction mixture into a suitable water-miscible sol-: vent and separated from the liquid by filtration, dccantation or other suitable means.

While the example above calls for molar quantities of alkali, only catalytic quantities of alkali, for example, about one per cent. by weight, are required for the phenol-formaldehyde reaction. It will be seen therefore that phenoland formaldehyde may be allowed to react to form the trimethylol compound in the presence of a small amount of alkali at which time the rest of the alkali may be added to form the salt.

' Many solvents are suitable for precipitating the salts of trimethylol phenol, c. g., methanol,- ethanol, n-propanol, 'isopropanol, tertiary butanol, secondary butanol, isobutanol, n-butanol, tertiary amyl alcohol, allyl alcohol disacetone alcohol, butyl carbitol, pyridine, 2-(2'-hydroxyethyl) -pyridine, phenyl cellosolve, acetone, acetonitrile, propionitrile, morpholine, diethylenetriamine, methylal, dimethyl cellosolve, dioxane,

etc. In general alcohols with no more than four carbon atoms are the most efficient precipitating agents and particularly those with two or three carbon atoms. The 4 preferred precipitating agents are ethanol, propanol, isopropanol and acetone. Of these, ethanol is most suitable from the point of view of low cost, availability and purity of the product obtained. Mixtures of the above precipitating agents also have been found to be very useful. Among the mixtures which are suitable are, by volume, 50-50 n-butanol and methanol, 50-50 methanol and acetone and 50-50 n-amyl alcohol and methanol.

The only metal hydroxides found to be su table for the preparation of salts of 2,4,6-tr1s- (hydroxymethyDphenols or trimethylol phenols according to this invention are sodium and barium hydroxides. While formaldehyde is mentioned above, equivalent amounts of paraformaldehyde may be used.

The following examples illustrate the preparation of the sodium and barium salts of trimethylol phenol or 2,4,6tris(hydroxymet hyl)- phenol:

Example I To 188 parts by weight (2 mols) of phenol were added 90 parts by weight (2.25 mols) of sodium hydroxide which had been previously dissolved in seventy parts by weight of water. The mixture was cooled and allowed to crystallize; 588 parts by weight (7.3 mols) of formalin (37.2% by weight formaldehyde) were added and the 4 mixture stirred. The temperature of the reaction mixture rose spontaneously to a maximum of 45 C. and then dropped slowly. The mixture was kept at room temperature fifteen to twenty hours, dehydrated under vacuum with heat until the temperature-in the flask rose to 45 C. and poured into several times its volume of ethanol. After 3-4 hours the resultant precipitate of sodium trimethylol phenate was filtered and dried.

Theoretical yield, 412 parts by weight.

Actual yield, 335 parts by weight or 81.3% of theory.

Example I] trimethylol phenate, after standing a few hours,

was filtered ofi, washed with acetone and inavacuum desiccator. Theoretical yield, 125.8 parts by weight. Actual yield, 97.9 parts by weight or 77.8% of theory.

Example III To 76.2 parts by weight (0.945 mol) of formalin were added while stirring 23.5 parts by weight (0.25 mol) of phenol and twelve parts by weight (0.33 mol) of sodium hydroxide, dissolved in fifteen parts by weight of water. The temperature of the reaction mixture was held at 30 C. or less fortwohours. The mixture was put in an oven for twenty-two hours at a temperature of 40 C. Next, 804 parts by weight of n-propanol was poured into the reaction mixture and themix stirred. The resulting precipitate of sodium trimethylol phenate was filtered ofi, washed with acetone and ether and dried in a vacuum desiccator.

Theoretical yield, 51.5 parts by weight.

Actual yield, 50.8 parts by weight or 98% of theory. l V

Other methods for making the sodium and barium salts of symmetrical trimethylol phenol are more specifically disclosed ,in my aforementioned copending application Serial No. 122,128. The latter application also discloses steps taken to identify the salts formed as being actually the ones claimed to have been obtained.

It is to be noted that, consistent with the rules of orientation, only those phenols possessing free reactive hydrogen atoms in all three positions ortho and para to the phenolic hydroxyl group can form trimethylol compounds, e. g. phenol, m-cresol and 3,5-xylenol. However, from. actual experiment, it has been found that 3,5-xylenol forms a product in which the salts of uniand bis(hydroxymethyl) compounds predominate along with resinous products. No evidence has been obtained of the formation of the salt of the tris(hydroxymethyl) compound. When m-cresol is used only low yields of the salts of tris(hydroxymethyl) compound can be obtained due to the fact that the resins are readily formed. From the examples given above, it will also be noted that the reaction may be carried out at various temperatures, the lower temperatures ranging at around 0 C; requiring areactiontim of severaldays while the reaction at temperatures around 60 C. takes place in several hours. However, temperatures of over 65 C. will cause undesirable side reaction.

The sodium and barium 2,4,6,-tris(hydroxymethyl) phenates may bereacted with other compounds to provide a class of primary polyhydrie alcohols with a wide range of applications in the chemical, plastics and coating arts. Notable;

where R represents a member of theclass con-- sisting of aliphatic, cycloaliphatic and aryl-substitutedaliphatic groups including theirhalcgensubstituted derivatives. The following. examples illustrate the preparation of these types of, compounds.

Example-IV i A: mixture of" 139; parts by weight iii-sodium 2;4,6--tris(hydroirymethyl)phenate, 126 parts by weight ofmethyl-iodide and 4 20 parts by weight of methanol was divided equally between three bottles. The-bottles were'sealedand placed; in an-oven-a t-fii'wf G: for about fifteen to-twenty hours. The bottles were cooled and opened; The methanol was boiled -oiT and the products were dissolved in a-myl alcohol: The amylalcohol' solution was 'washediwith' an aqueous, solution of" sodium carbonate; The amyl alcohol was distilled off under vacuum. The product, l-methoxy- 2,4,6-tris (hydroxymethy-l) benzene was a viscous light brown syrup. r i

Yield=118 parts by weight- 'I,'l'1eory= 1 34-partsby-weight Methoxyl content =15,;33.% 15.70% Theory- .66% r 1 Ezcdmple, v.

. To;twenty.-one,parts byweight-of sodium 2,4,6

trisrihydroxymethyl) phenate placed in-a; bottle,

eightyparts; by; weight of; methanol andgsixteenparts by: volume of methyl iodide-,1 were added Th bottle was sealed; andheatedfor sixhours at: 68?. C; The reaction mixture wasallowed to stand'for two' days at room temperature. The

methanol was evaporated and the product esterifled using acetic anhydride andpyridine as esterifying agent. The, ester, 1 methoxy+2.,4-,6.-tris- (aceterymethylibenzene, was-distilled the benzyl chloride.

Saponification equivalent;10f7;106.4 Theory=. 1;08 j Carbonic? I 59.51%. Theory,=.5.9.2

Hydrogen;

Eound1=5.96,.6.01.;

Theory=6.22

Example VI To 210 parts: by weightv of sodium 2,4;6-tris- (hydroxymethyl)phenate-was added a solutionof 130 parts-by weight ofyall yl bromide: in 475 parts by weight of methanol. The mixture was refluxed with:stirring:for.two hoursr The methanol wasdistilledr 'oif' under vacuum and amyl alcohol added. I The'amyl al'coholi solution was washed with a solution of saturated sodium carbonatepotassium chloride-and was dried over anhydrous sodium sulphate. Thev a yl alcohol was removed under vacuum. The product, 1 -allyloxy-2,4 ,6- wasa brownsyrup.

tris (hydroxymethyl) benzene,

Yield=l40 parts by weight. Theory= 224.

- Example VII Same as. Example VI'except that the mixture. was heated for two and one-half to three hours,

at 45 C. (and then at C.) for two hours. For a number of reactions of this example the conversionto the allyl ether-was found torangejrom percentto 10.0 per cent.

. Example TIIII Forty-two parts by'weight, of. the sodium 214,6 5 -tris(hydroxymethyl)phenate was placed. in a.

bottle with forty parts by volume of a 2.5 per cent'solution of sodium' hydroxide. 26.6 parts by-weight of'benzyl chloride was addedas well as thirty-two parts by weightv of methanol. The reaction ingredients were. shaken at. 55 Cffor forty-eight hours; bottle were poured into 200 300 parts by weight of 'hot'water, heated for ten to fifteen minutes and stirred. I When, stirring. was stopped, the product separated out as an oily. layer. The washed product was dissolved in acetone, fil tered, and the water and, acetone distilledofl. The product; methylibenzene,

retical yield was 54.8 partsby weight-,the actual yield was 38.92 parts by weight or, 2.71 per-centv Example. VIII wasrepeated using nineteen parts .1 by: weight of z-methallyl chloride in place,

V The'methanol which" had been added in Example VIII: to increase the. solubility of. the benzyl chloride in'the reaction,

of: thev benzyl chloride.-

mixture Was'notemployed. Theproduct, 1-'(2'- methallyloxy) 2,4 ,6 tris(hydroxymethyl) hen: viscous; almost solid brown zene, was a very syrup; The actual yield was 32.92 parts. by we ght as. compared with the theoretical 47.6 partsby weight or=a.= 69 per cent new: j 11 Emmple X" Example VIIIT was again repeated; using 23.31

parts by weight 2,3-dichloropropene-l in lieu of cent of the theoretical value of, 51;;7iparts,lc'iyf:

.75. ight. I

The; cooled contents of the.

' 1'-benZ yloXy.-2,4,6-tris (hydroxywas a brown syrup. The.theo-;

Methanol was not. used; Theproduct; 1- (2 "-chloroallyloxy) +2,4,6-t1'is (hydroxymethyl) benzene was a viscous brown syrup.

7 Eaample XI 1 H 7 Exam le VIII was repeated using 23.3 partsvby weight of 1,3-dichloropropene-1 in place of benzyl chloride and without the use of methanol. The 1-(3 chloroallyloxy) 2,4,6-tris(hydroxymethyl) benzene was a viscous brown syrup. The yield was 40.82 parts by weight or 79 per cent of the theoretical value of 51.7 grams.

Example XII Example VIII was again repeated using 28.8

parts by weight of n-butyl bromide in place of the benzyl chloride along with forty parts by weight of methanol. The yield of l-butyloxy- 2,4,6-tris(hydroxymethyl) benzene as a viscous brown syrup was 27.85 parts by weight or 57.8% of the theoretical value of forty-eight parts by weight.

Example XIV One hundred and ninety-two parts by weight of the sodium salt of trimethylol phenol was dissolved in water and 49 parts by weight of dimethyl sulphate added. The mixture was stirred for two hours,71 parts by weight of sodium hydroxide and 92 parts by Weight of dimethyl sulphate added and stirring continued for about 12 hours. The temperature of the mixture was then raised to boiling and extracted while hot with n-amyl alcohol. The product, trimethylol anisole, was obtained ina yield of 135 parts by weight, or a 73% of theory. All of the product was refluxed several hours "with an excess of acetic anhydride. The acetic acid and excess acetic anhydride was removed by heating under vacuum. The resulting ester was Washed twice with water and distilled at a temperature of 170-180 C. under a reduced pressure of 1-2 mm.

of mercury to yield purified'tri-(acetoxymethyl) anisole.

While ethers of 2,4,6-tris(hydroxymethyl)-i phenols have been found to be very useful, they are rather expensive to produce in the pure state because of the separation process. It has been found that for many applications in connection with making the presently claimed compositions, the. ethers of the tris(hydroxymethyl)phenols can tolerate certain amounts of the ethers of 2- (hydroxymethyl) phenol, l -(hydroxymethyl) phenol, '2,6-bis(hydroxymethyl)phenol and 2,4-bis- (hydroxymethyhphenol. It has been further found that .the presence of the ethers of the uniand bis-compounds doesnot detract appreciably from the beneficial results obtained. The amount of the tris(hydroxymethyl)phenyl ethers present in the mixture may be varied and may be present in the major proportion of more than fifty per cent by weight. However, percentages ranging from, e. g., to 90 per cent, may be present. In general, if at least 2.5 mols of formaldehyde are used to each mol of phenol, the major proportion of the reaction product'will be the tris(hydroxymethyl)compound. Consequently, the corresponding ether mixture will predominate'in the ether of the tris(hydroxymethyl)phenol.. The

formula v,ofsuch mixtures may be represented as follows:

H (CHiOEUn Example XV Formalin in the amount of 980 parts by weight (12 mols) of 37.5% solution of formaldehyde was added to 376 parts by weight of phenol and mixed thoroughly. A solution of 176 parts by weight of sodium hydroxide in 200 parts by weight of water was added slowly to the mixture with cooling. The reaction mixture was then placed in an oven at 40 C. for fifteen to twenty hours. Analysis showed that 95.6 per cent of the formaldehyde had reacted. The above phenate solution was placed in a flask equipped with a stirrer. To the solution was added 326.5 parts by weight of allyl chloride and the whole stirred vigorously and heated at 60 C. for about two hours. The etherification reaction ran to about ninety-five per cent of completion.

Example XVI Three hundred and fifty parts by weight of phenol and 900 parts by weight of 37.3% aque ous formaldehyde were mixed with stirring. To the solution was added 164 parts by weight of so dium hydroxide in parts by Weight of water and the whole reacted for six and one-half hours at 40 C. Analysis showed that 86.6 per cent of the formaldehyde had reacted to give about sixty per cent sodium tris-(hydroxymethylJphenate along with the uniand bis(hydroxymethyl) phenates. Three hundred and three parts by weight of allyl chloride was added and the mixture reacted in a pressure reactor at 60 C. for three hours with vigorous stirring. Analysis showed that 98.7 per cent of the allyl chloride reacted. The aqueous layer was drawn oil and the organic layer dehydrated by heating under a vacuum. The yield was 650 parts by weight equal to three in the major proportion.

Example XVII Formalin in the amount of 980 parts by weight (12 mols) of 37.5% solution of formaldehyde was added to 376 parts by weight of phenol and mixed thoroughly. A solution of 176 parts by weight of sodium hydroxide in 200 parts by weight of water was added slowly to the mixture with cooling. The reaction mixture was then placed in an oven at 40 C. for fifteen to twenty hours. Analysis showed that 95.6 per cent of the formaldehyde had reacted. The above phenate solution was placed'in' a flask equipped with a stirrer. To the solution was added 326.5 parts by weight of allyl chloride and the whole stirred .vigorously and heated at 60 C. for about two hours. The etheri- Three hundred and fifty parts by weight of phenol and 900 parts by weight of 37.3% aqueous phenates.

formaldehyde were mixed with stirring. .Toithe solution was added 164 parts by-TWeightofifsO- dium hydroxide in 170 parts by weight offwa't'er 1 and the whole reactedffor six and o'lne-fhalff hours .,at..40 C Analysisshowed that 86.6 per centof ..,the;formaldehyde had reacted to give about sixty per cent sodium tris(hydroxymethyl phenate along with the uniand bis(hydroxymethyl Three. hundred-and three parts by ,vveight of allyl chloride was added and themix- (hydroxymethyl) phenyl ether, then polyglycol ethers areof "necessity formed, The excessalkylene oxide, above three mols, reacts with thehy- ,droxylg oup' oi the already formed glycolether to give polyglycol ether groups. Example XX ,Qnehundred parts .by weight of leallyloxyf 2,156 trisihydroxymethyl) benzene, ten parts by .ture reacted insa pressurereactor, at 60 CQior three hours with vigorous stirring. Analysis showed that 98.7 percent of theallylchloride reacted. The aqueouslayer was-drawn off and gthegorganic layer dehydrated by heating under a vacuum. The yield was 650 parts by weight of the .:;allyl ethers of the mixed unie, bis-i and=-tris(hy- ,droxymethyl) phenols with the tris compound beingpresent as the major component. U

Example XIX 'Ihree hundred andthirty-two parts by weight of phenol (96% pure) and 835 parts by weight ,of

I j Otheroxides suchasubutylene oxide, ,styrene a 36.4% aqueous solution of formaldehyde and .160 parts by weight of sodium hydroxide, Vin- 167 parts by weightof waterwere mixed and reacted for sevenand one-half hours at-l40F ,C. at;whioh .tim,e83.5 per cent of the formaldehyde; had rephenyl ethers may be converted to ether groups by reacting (1) an aklylene oxide corresponding to the general formula ,R'-,cH-' oH1 where R represents a member of the class consisting of hydrogen, aliphatic, alkoxyaliphatic, aliphatic-substituted aryl, aryl, aryl-substituted aliphatic, and aryloxyaliphatic groups with (2) a tris(hydroxy methyl) phenyl ether corresponding'to' the general formula 1' 1112011 where R has the meaning given above.

Theoretically, if three mole of alkylene oxide, e. g.. propylene oxide, are employed for each mol of tris(hydroxymethyl) phenyl ether, each of the three hydroxymethyl groups wouldcarry. a hy- I L The hydroxy groups of the tris(hydroxymethyl) I the mixture.

weight of one. normal sodium hydroxide and sixty lpartsfby weight of ethylene oxidewere heated in 'fasealed container for seventy-two hours at'40j C. ."The product was .a very light straw colored, "honey-likdmaterial which was somewhat-soluble inwater. I The productwwas .a polyethylene. glycol ether derivative of the IgaIIyIQXy Z'Afii-tris (hydroxymethyl), benzene wherein an average of one molecule ofQethylene oxide has reacted.- withi'eaoh hydroxymethyl group.

oxide,. gly.cidyl phenyl ether, glycidyl allyl ether,

and butadiene monooxide .a'mon'gjothers m filso be re'aoted to give analogous compounds allfiof -which are, useful as plasticizers for various resins. is Here again. from an economical point off'view,

it is advantageous to use reaction products vproducedfrom a mixture o f..the.uni-, bis- .andtrishydroxymethyll compounds with the "tri's(hydroxymethyl) compound present in an amount of over fiftyper: cent as in thesfollowing examples. However; .I do not intend-to be. limited to this .per cent'sincesmaller (e.g.,,1 0-to 40-per1cent) or larger per 'centsof. the=total of uniand bis- (hydroxymethyl) compounds corresponding. to the general formula. I

. 1 where has the ,meaning given. above and '12. is an integer equal ,toirom l;to '2, inclusive, .may also beus ed without departing-from the scopeof theinvention. 1 i

" ExamplelXXl Eighty-six parts by weight .f of a mixture .of 1 allyloxy 2. (hydroxymethyhhenzene, ,1.-a11y1 .oxy-i (hydroxymethyl) benzene l -allyloxy-z, 4- bisihydroxymethyl) benzene, ll-allyloxy zfii-bis- (hydroxymethyl) benzene, and l. -,-allyloxy2,4,6- tris (hydroxymethyl) benzene wherein the mixture as .a whole contains an 'averageof 2.6hydroxymethyl groups for. each benzene nucleus, forty-two parts by weight of propylene oxide and a trace ofsodium hydroxide were heated overnight (about 16 hours) at 60 C. in a-sealed container. ,The reacted mixture was filtered and neutralized with acid, washedseveral-times with water and dehydrated under a vacuum-to yield a clear honey-colored liquid. .Thecompound was the;reaction product of one molecule of propylene oxide "1 or. each hydroxymethyl group; present, in

Example XXII ,Eighty-sixparts by weight "of a mixture'of the alloxy-, uni-,; bis+, and.tris(hydroxymethyl) "benzenes, a tracejof sodium hydroxide and twentyriine parts" by weight, of propylene-.oi'cide were placed in a sealed bottle and heated at 603p. for sixteen hoursQ The reaction. mixture was neutralized with hydrochloric: acid and'the organic oxide.

layer separated, washed several times with water and dehydrated under aIVacuumJ The product wasja straw-colored syrup in which an average of 0.4-0.5 mol of propylene oxidehas reacted for each hydroxymethyl group.

Example XXIII The l (2 hydroxyethyloxy) 2,4,6-tris(hydroxymethvl) benzene was first prepared by reacting about eighteen parts by weight of sodium 2,4,6-tris(hydroxymethyl) phenate with fourteen 'parts by weight of ethylene bromohydrin. The

reactants were dissolved in forty parts by weight of water and heated at 40 C. for about three and one-half hours to give a pale, straw-colored water-soluble svrup. .The product was refluxed with, about eighteen parts by weight of propylene oxide for seven hours Two. parts, by weight of sodium hydroxide in five parts by weight of water was added as a catalyst. At'completion of .the

reaction, the sodium hydroxide wasneutralized and the mixture dehydrated under a vacuum.

The salt formed by neutralization of the catalyst was filtered off leaving a viscous, very pale- 'colored syrup in which approximately 0.65-0.70

mol of propylene voxide'has reacted for each hydroxyl group present in the 1;(2 -hydroxyethyloxy) -2,4,6-tris(hydroxymethyl) benzene.

Example XXI V- A mixture of the alloxyuni-, bis-, and tris- (hydroxymethyl) -benzenes was treated with found very useful in 'plasticizing alkyd resins,

as wax modifiers, surface active v agents and humectants. They are compatible with polyvinyl acetals, polyvinyl alcohol, phenol-aldehyde resins, etc., and can be used to modify the properties of these resins. s

It will, of course, be apparent to those skilled in the art that instead of using the alkylene oxides employed in the foregoing examples, other alkylene oxides, many examples of which have been given above and in theformulas appearing in the application, may be employed without departing from the scope of the invention.

In addition, the molar ratioof the alkylene oxide and the particular methylol phenol ether employed may also be varied within'wide limits. Thus, although it is preferable to employ at least the same number of mols of alkylene oxide as there are hydroxyl groups around the benzene nucleus,it will be apparent that smaller molar amounts of the alkylene oxide may also be used whereby it is possible to obtain derivatives whereby some of the hydroxyl groups will not be replaced with the residue from the alkylene Thus, on a molar basis I may use, for example, from about 1 to 3, or even as high as 6 mols or more of the alkylene oxide per mol of the methylol phenyl ether. The tendency towards resinification ofthe trimethylol phenyl "ethers is low due to the fact that the phenolic hydroxyl group is etherified. This permits the use of higher reaction temperatures above that 12 possible wherethe phenolic hydroxyl group is not etherified. Y

The conditions of reaction whereby the reaction products, are obtained may also be varied and the reactionmay be carried out attemperatures ranging, for example, from room temperature to as high as C. or somewhat higher.

The" claimed compositions of matter are useful as intermediates in the preparation of other materials particularly esters thereof whereby esterification can take place of the hydroxyl groups of the alkylene oxide residue and of any hydroxyl groups remaining from the original methylol phenyl ether, to produce esters which are useful, for instance, as plasticisers for various resins, particularly the vinyl halide resin e. g., polyvinyl chloride, copolymers of vinyl chloride and vinyl .acetate, etc. The compositions herein claimed are compatible, with a number of resins, for example, polyvinyl acetals,

polyvinyl alcohol, phenol-aldehyde resins, etc., and can be used to modify the properties of these resins. i

Although it is difiicult'to isolate individual compounds as the result of the reaction of methylol-phenyl ether with the alkylene oxide, the claimed compositions of matter are definite mixtures which can be'reproduced at will following'ess'entially the same conditions in each case. Their character and'compositio'ns can be determinedby ascertaining the number of mols of alkylene oxide which have reacted with the methylol phenol ether.

What I claim as new and desire to secure by Letters'Patent of the United States is:

l. A composition of matter comprising the product of reaction at a temperature ranging up to 100 C. ofa mixture of ingredients com prising (1) a methylol phenol etherv corresponding to the general formula:

HO CH? CHzOH where R, represents a member of the class consisting of aliphatic, cycloaliphatic, aryl-substituted aliphatic groups, and halogen-substituted derivatives of the aforesaid aliphatic groups, and (2) an alkylene oxide corresponding to the general formula:

where R is a member selected from the class consisting of hydrogen, aliphatic, aryl, alkoxyaliphatic, aliphatic-substituted aryl, aryl-substituted aliphatic, and aryloxyaliphatic radicals.

2. A composition of matter comprising the products of reaction at a temperature ranging up to 100 C. of a mixture of ingredients comprising .(1) a mixture of methylol phenol ethers comprising (a) a methylol phenol ether corresponding to the general formula:

H0 0112- CHQOH l CHzOH where R represents a member of the class consisting of aliphatic, cycloaliphatic, aryl-substituted aliphatic groups, and halogenated derivatives of the aforesaid aliphatic groups, and n is an integer equal to from 1 to 2, inclusive, and (2) an alkylene oxide corresponding to the general formula:

where R is a member selected from the class consisting of hydrogen, aliphatic, aryl, alkoxyaliphatic, aliphatic-substituted aryl, aryl-substituted aliphatic, and aryloxyaliphatic radicals.

3. A composition of matter comprising the product of reaction at a temperature ranging up to 100 C. of a mixture of ingredients comprising (1) a methylol phenol ether corresponding tothe general formula:

no 0112f -omon H H UHEOH HOCHf- CHzOH where R represents a member of the class consisting of aliphatic, cycloaliphatic, aryl-substituted aliphatic groups, and halogen-substituted derivatives of the aforesaid aliphatic groups, and (2) glycidyl allyl ether.

5. A composition of matter comprising theproduct of reaction at a temperature ranging up to 100 C. of a mixture of ingredients comprising (1) a methylol phenol ether corresponding to the general formula:

HOCHr- CHzOH l CHzOH where R represents a member of the class consisting of aliphatic, cycloaliphatic, aryl-substituted aliphatic groups, and halogen-substituted derivatives of the aforesaid aliphatic groups, and (2) 3,4-epoxybutene-1.

6. A composition of matter comprising the product of reaction at a temperature ranging up to C. of a mixture of ingredients comprising (1) a methylol phenol ether corresponding to. the general formula:

HooH2 omon 7 emon where R represents a member of the class consisting of aliphatic, cycloaliphatic, aryl-substituted aliphatic groups, and halogen-substituted derivatives of the aforesaid aliphatic groups, and (2) ethylene oxide.

I 7. A composition of matter comprising the product of reaction at a temperature ranging up to 100 C. of a mixture of ingredients comprising 1 allyloxy 2,4,6 tris(hydrox ymethyl) benzene and (2) propylene oxide.

8. A composition of matter comprising the product of reaction at a temperature ranging up to 100 C. of a mixture of ingredients comprising 1 allyloxy 2,4,6 tris(hydroxymethyl)benzene and (2) glycidyl allyl ether.

9. A composition of matter comprising the product of reaction at a temperature ranging up to 100 C. of a mixture of ingredients comprising 1 allyloxy 2,4,6 tris(hydroxymethyl) benzene and (2) 3,4-epoxybutene-1.

10. A composition of matter comprising the product of reaction at a temperature ranging up to 100 C. of a mixture of ingredients comprising 1 allyloxy 2,4,6 tris(hydroxymethyl)benzene and (2) ethylene oxide.

11. A composition of matter comprising the product of reaction at a temperature ranging up to 100 C. of a. mixture of ingredients comprising l) 1 methoxy 2,4,6 tris(hydroxymethybbenzene and (2) propylene oxide.

ROBERT W. MARTIN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,976,677 Wittwer Oct, 9, 1934 2,213,477 Steindorff et a1. Sept. 3, 1940 2,495,232 Drisch et a1. Jan. 24, 1950 2,499,365 De Groote et a1. Mar. 7, 1950 2,503,726 Greenlee Apr. 11, 1950 

1. A COMPOSITION OF MATTER COMPRISING THE PRODUCT OF REACTION AT A TEMPERATURE RANGING UP TO 100* C. OF A MIXTURE OF INGREDIENTS COMPRISING (1) A METHYLOL PHENOL ETHER CORRESPONDING TO THE GENERAL FORMULA: 